JPH10186722A - Electrostatic image developing toner, image forming method, toner resin composite and manufacture of toner resin composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic image developing toner having a wide fixable temperature area, excellent in reproducibility of dots, and capable of forming a stable image. SOLUTION: In an electrostatic image developing toner containing at least a binder resin and a coloring agent, the binder resin in the toner substantially contains no tetrahydrofurane(THF) insoluble component, the hydroxyl valence of the low molecular weight component corresponding to the molecular weight area of 50,000 or less is 20 (mgKOH/g) or less in the molecular weight distribution of gel permeation chromatography(GPC) of THF soluble component, and the high molecular weight component corresponding to the area exceeding the molecular weight of 50, 000 is formed of a polymer obtained by the reaction of a mixture of a lower molecular weight polyester and a low molecular weight wax represented by the formula R-Y with a diisocyanate compound and/or a polyisocyanate compound. In the formula, R represents hydrocarbon group, and Y represents hydroxyl, carboxyl, alkylether, ester, or sulfonyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for visualizing an electrostatic latent image in an image forming method such as electrophotography, electrostatic printing and magnetic recording. In particular, a toner for developing an electrostatic image used in a fixing method of heating and fixing a visible image formed by a toner to a recording material, an image forming method using the toner, and a resin composition used for the toner and the same It relates to a manufacturing method.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
A number of methods are known, as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, but generally, a photoconductive substance is used. An electric latent image is formed on the photoreceptor by various means, then the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper. The toner is fixed by pressurization or solvent vapor to obtain a copy, and the remaining toner not transferred onto the photoreceptor is cleaned by various methods, and the above-described steps are repeated.

In recent years, such copying apparatuses have been strictly pursued for smaller size, lighter weight, higher speed, and higher reliability, and as a result, the performance required for toner has also become higher. ing. For example, various methods and apparatuses have been developed for the process of fixing a toner image on a sheet such as paper, but the most common method at present is a heat compression method using a heat roller. The heat compression bonding method using a heat roller performs fixing by allowing the toner image surface of a sheet to be fixed to pass through the surface of a heat roller having a surface formed of a material having releasability with respect to toner while contacting the surface under pressure. . In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the heat efficiency when fixing the toner image on the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in high-speed electrophotographic copying machines.

However, in the above-described heat roller fixing which has been frequently used, (1) there is a so-called wait time during which the image forming operation is prohibited until the heat roller reaches a predetermined temperature.

(2) The optimum temperature of the heating roller is set in order to prevent defective fixing due to the fluctuation of the temperature of the heating roller due to the passage of the recording material or other external factors and the transfer of toner to the heating roller, ie, the so-called offset phenomenon. In order to achieve this, the heat capacity of the heating roller or the heating element must be increased, which requires a large amount of electric power and causes a rise in the temperature inside the image forming apparatus.

(3) Since the pressure roller has a lower temperature than the fixing roller, when the recording material is discharged through the heating roller, the recording material and the toner on the recording material are cooled slowly. The toner becomes highly sticky, and in combination with the curvature of the roller, a paper jam may occur due to offset or entanglement of the recording material. Etc. are not fundamentally solved.

JP-A-63-313182 by the present applicant
In Japanese Patent Application Laid-Open Publication No. H10-209, an image with a short wait time and a low power consumption is fixed by a fixing device that heats a toner visible image through a heat-resistant sheet moved by a low-heat-capacity heating element heated in a pulse shape and fixes the recording material. A forming device has been proposed. Similarly, Japanese Patent Application Laid-Open No. Hei.
No. 7582 discloses a fixing device for heating and fixing a visible image of a toner to a recording material via a heat-resistant sheet.
A fixing device has been proposed in which the heat-resistant sheet has a heat-resistant layer and a release layer or a low-resistance layer to effectively prevent the offset phenomenon.

However, in order to realize a fixing method that has a short wait time and low power consumption while achieving excellent fixability of a toner-visible image to a recording material, prevention of offset, and the like, a fixing device as described above is used. In addition, the characteristics of the toner are greatly affected.

Conventionally, a method using a toner having two peaks in the molecular weight distribution as a binder resin of the toner, and a low molecular weight wax are typified by the idea of giving the toner itself good fixability and offset resistance. A method of adding a low molecular weight polyolefin polymer to a toner has been proposed.

The method described in, for example, JP-A-56-1
6144, JP-A-2-23569, JP-A-63-127254, JP-A-3-26831, JP-A-62-9356, JP-A-3-725
Japanese Patent Application Laid-Open No. 52-3304 and Japanese Patent Application Laid-Open No. 52-330
No. 5, JP-A-57-52574, JP-A-58-58574
JP-A-215659, JP-A-60-217366, JP-A-60-252361, JP-A-60-2
No. 52362 is disclosed.

However, simply using a binder resin having two peaks in the molecular weight distribution or including a certain release agent in the toner does not improve the fixing property and the offset resistance to some extent. Although it can be seen, not only does the binder component in the toner cause non-uniformity, but also hinders the dispersion of other components such as wax, and uneven distribution and release of specific components are likely to occur. This may cause fusion to a photosensitive member or filming.

On the other hand, Japanese Patent Application Laid-Open No. 62-78569 proposes a toner using a polyester having a saturated or unsaturated aliphatic hydrocarbon group having 3 to 22 carbon atoms in a side chain. Also, JP-A-63-225244
Japanese Patent Laid-Open Publication No. HEI 9-125605 proposes a toner using two types of polyester as a binder resin.

However, even in these toners, poor compatibility between the polyester resin and the polyolefin wax tends to cause poor dispersion of the polyolefin wax during the production of the toner. Many mixed in,
This impairs the chargeability of the toner, deteriorating the developability, and hindering the durability and storage stability of the toner. In particular, when two types of polyesters having different melt viscosities are used, the dispersibility of the polyolefin wax in the polyester resin having a low viscosity is not sufficient, and the above-mentioned problem becomes remarkable. In addition, it causes cleaning failure, fusion to a photosensitive member or the like, filming, and the like, and causes a problem in matching with an image forming apparatus.

Therefore, for example, the compatibility of the toner constituent components,
In order to improve the dispersibility, when the kneading conditions at the time of melt kneading during the production of the toner is strengthened, the molecular weight of the toner at the time of toner decreases due to the breaking of the molecular chain of the binder resin in the toner due to kneading, There are problems such as deterioration of the offset resistance, particularly the hot offset on the high temperature side.
Further, when a large amount of wax is added in order to exert a sufficient effect on the offset resistance, blocking resistance deteriorates and dispersion of the wax deteriorates, and the surface of the toner carrier such as a carrier or a sleeve is deteriorated. Contamination is promoted, the image is deteriorated, and this poses a practical problem.

On the other hand, Japanese Patent Application Laid-Open Nos. 2-129653 and 3-46668 propose a toner using a polyester obtained by treating a polyester resin with an acid or an alcohol as a binder resin.

Although these toners have some improvement in fixing property and charging property, they have little contribution to improvement in dispersibility of polyolefin wax because the monoalcohol used has only 10 carbon atoms in the alkyl group. Conversely, the introduction of the monoalcohol softens the polyester resin and the plasticizing effect of the unreacted alcohol causes new problems such as high-temperature offset resistance and storage stability, and durability of the toner during long-term use.

Further, in Japanese Patent Application Laid-Open No. Hei 7-36210,
There is disclosed a technique in which a long-chain primary alcohol and a polyisocyanate are used during the production of a toner, melt-mixed with a binder resin having a hydroxyl group, and grafted. However, in this case, since the entire binder resin is plasticized, low-temperature fixing is improved, but offset resistance is deteriorated. That is, the effective fixing area is not expanded. Further, an unpleasant odor due to unreacted polyisocyanate is not preferable for the toner.

In Japanese Patent Application Laid-Open No. 7-56386,
Although a technique of adding a reaction product of a long-chain alcohol and an aromatic diisocyanate to a toner is disclosed, the effective fixing area is not expanded similarly to the above. Further, since the dispersibility in the toner is not taken into consideration, high-definition development and matching with the image forming apparatus become insufficient.

The various properties required for the above-mentioned toners are often reciprocal to each other, and it is more and more desirable in recent years to satisfy both of them with high performance. Research has been conducted on comprehensive responses that include, but there is still not enough.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to significantly improve the disadvantages of the prior art, improve the fixability and the anti-offset property, and stably realize a high-quality image for a long period of time. And a toner for developing an electrostatic image capable of being highly applied to an electrophotographic process which does not adversely affect a photoreceptor or a toner carrier, an image forming method using the toner, a resin composition for the toner, and a method of manufacturing the same Is provided.

[0021]

Means for Solving the Problems The present inventors have made intensive studies and, as a result, specified the structure of the resin composition, the structure of each polymer component constituting the resin composition, and the method for producing the same, thereby making it extremely possible. The present inventors have found that they have a wide fixing temperature range, are excellent in dot reproducibility, and can form stable and good images, and have completed the present invention.

That is, the present invention relates to an electrostatic image developing toner containing at least a binder resin and a colorant,
The binder resin of the toner is (a) substantially free of tetrahydrofuran (THF) -insoluble matter, and (b) the molecular weight distribution of THF-soluble gel permeation chromatography (GPC) is as follows: i) molecular weight of 50,000 The hydroxyl value of the low molecular weight component corresponding to the following region is 20 (mgKOH / g) or less; ii) The high molecular weight component corresponding to the region exceeding the molecular weight of 50,000 is a low molecular weight polyester and a low molecular weight having the following general formula. RY which is a polymer obtained by reacting a wax mixture with a diisocyanate compound and / or a polyisocyanate compound [R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] It is a toner for developing an electrostatic image.

Further, the present invention provides at least a charging step of applying a voltage to a charging member from the outside to charge a member to be charged, and a step of forming an electrostatic charge image on the charged member to be charged.
A developing step of developing an electrostatic image with toner to form a toner image on a member to be charged, a transfer step of transferring the toner image on the member to be charged to a recording material, and heating and fixing the toner image on the recording material A fixing step, wherein the toner contains at least a binder resin and a colorant, and the binder resin of the toner contains (a) a substantially tetrahydrofuran (THF) -insoluble component. (B) In the molecular weight distribution of gel soluble permeation chromatography (GPC) of the THF-soluble component, i) The hydroxyl value of the low molecular weight component corresponding to the region of molecular weight of 50,000 or less is 20 (mgKOH / g) or less. Ii) a mixture of a low-molecular-weight polyester and a low-molecular-weight wax having the following general formula and a diisocyanate compound; and / or Is a polymer obtained by reaction with a polyisocyanate compound, RY [R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] The image forming method is characterized in that:

Further, the present invention provides at least a charging step of applying a voltage to a charging member from the outside to charge a member to be charged, and a step of forming an electrostatic charge image on the charged member to be charged.
A developing step of developing the electrostatic image with toner to form a toner image on the member to be charged; a first transfer step of transferring the toner image on the member to be charged to the intermediate transfer member; An image forming method comprising: a second transfer step of transferring a toner image to a recording material; and a fixing step of heating and fixing the toner image on the recording material, wherein the toner contains at least a binder resin and a colorant. The binder resin of the toner is (a) substantially free of tetrahydrofuran (THF) -insoluble matter, and (b) the molecular weight distribution of THF-soluble gel permeation chromatography (GPC) is as follows: The low molecular weight component corresponding to the region having a molecular weight of 50,000 or less has a hydroxyl value of 20 (mg KOH / g) or less; ii) the high molecular weight component corresponding to the region having a molecular weight of more than 50,000 is a low molecular weight polyester or RY [R: a hydrocarbon group, which is a polymer obtained by reacting a mixture of a low molecular weight wax having the general formula with a diisocyanate compound and / or a polyisocyanate compound. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] The image forming method is characterized in that:

The present invention also relates to a resin composition for a toner used for a toner for developing an electrostatic image, wherein the binder resin component of the resin composition for a toner comprises: (a) tetrahydrofuran (THF) -insoluble matter; 30wt
(B) In a molecular weight distribution of gel permeation chromatography (GPC) of a THF-soluble component, i) a low molecular weight polymer having a hydroxyl value of 20 mg KOH / g or less and a molecular weight of 50,000 or less; and ii) a low molecular weight. A toner resin composition comprising a polymer obtained by reacting a mixture of a polyester and a low molecular weight wax having the above general formula with a diisocyanate compound and / or a polyisocyanate compound.

Further, the present invention relates to a method for producing a resin composition for use in an electrostatic image developing toner, wherein the resin composition comprises a mixture of a low molecular weight polyester and a low molecular weight wax having the following general formula: By reacting the compound and / or the polyisocyanate compound, (a) tetrahydrofuran (THF) insoluble matter is 30 wt.
(B) in a molecular weight distribution of gel-permeation chromatography (GPC) of a THF-soluble component, i) a low molecular weight polymer corresponding to a region having a molecular weight of not more than 50,000 and having a hydroxyl value of not more than 20 mgKOH / g; ii) A high-molecular-weight polymer RY [corresponding to a region exceeding a molecular weight of 50,000 obtained by reacting a mixture of a low-molecular-weight polyester and a low-molecular-weight wax having the following general formula with a diisocyanate compound and / or a polyisocyanate compound. R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] At the same time.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrostatic image developing toner of the present invention comprises a low molecular weight polymer component (A) having a low hydroxyl value, a low molecular weight polyester (B) and a low molecular weight wax (C) having a specific structure. And a diisocyanate compound and / or a polyisocyanate compound to obtain a high molecular weight polymer component (D). It is possible to achieve both. Also,
The hydroxyl value of the low molecular weight polymer component (A) is 20 mg KOH
/ G or less, and by introducing a long-chain alkyl group into the high-molecular-weight polymer component (D), the low-temperature fixing and the offset resistance are further improved, and the wax component and other additives in the binder resin component are added. Since the dispersibility of the agent is improved, not only the charging characteristics of the toner are good, but also the matching property with the image forming apparatus is excellent, and various problems such as poor cleaning and toner fusion are prevented beforehand. Further, in terms of toner production, production efficiency is improved.

The low molecular weight polymer component (A) contained in the binder resin component according to the present invention has a hydroxyl value of 20 mg KOH / g or less, more preferably 1 mg or less, as exhibited by the polymer component (A).
0 mgKOH / g or less, particularly preferably 5 mgKOH / g.
The composition is adjusted to be OH / g or less.

The low molecular weight polymer in the binder resin component has a relatively high molecular chain mobility, and therefore has a hydroxyl value of 10
If it exceeds mgKOH / g, the charging relaxation rate increases, and the frictional charging of the toner becomes insufficient. Further, since the uniform dispersion of the wax component such as polyolefin is inhibited, the charging characteristics of the toner are significantly deteriorated.

In the present invention, the hydroxyl value of the resin composition,
The acid value is measured by the following method.

For the measurement of the hydroxyl value, first, a sample was taken 100 times.
The mixture is precisely weighed in a 50 ml volumetric flask, 50 ml of xylene is added, and the mixture is dissolved in an oil bath at 120 ° C. 50 ml of xylene is taken as a blank in another volumetric flask, and the same operation is performed thereafter.

After dissolution, 5 ml of a mixed solution of acetic anhydride / pyridine (1/4) is added. After heating for 3 hours or more, the temperature of the oil bath is raised to 80 ° C., a small amount of distilled water is added, and the temperature is maintained for 2 hours. Thereafter, the mixture is left to cool, and the flask wall is thoroughly washed with a small amount of an organic solvent. A phenolphthalein (methanol solution) indicator was added, and a 1 / 2N KOH / methanol titrant was used.
Potentiometric titration is performed, and the OH value is determined from the following equation.

OH value = 28.05 × f × (T _b −T _S ) / S + AS S: Sample amount (g) T _S : Sample titer (ml) T _b : Blank titer (ml) f: Titrant Factor A: Acid value of sample On the other hand, the acid value is measured according to “JIS K1557-197.
According to “0”, the sample is weighed, dissolved in a mixed solvent, and added with water. This solution was made 0.1 N-Na using a glass electrode.
Perform a potentiometric titration with OH to determine the acid value.

As the polymer component (A) according to the present invention, known polymers can be used as long as the hydroxyl value is 20 mgKOH / g or less, and polyester resins and vinyl resins are suitable for toner. It is.

The polyester resin preferably used for the polymer component (A) according to the present invention is as follows.

The composition of the polyester resin is 4% of all components.
5 to 55 mol% is an alcohol component, and 55 to 45 mol%.
mol% is the acid component.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (A);

[0038]

Embedded image

Diols represented by the formula (b):

[0040]

Embedded image And the like.

Examples of the divalent carboxylic acid containing 50 mol% or more of the total acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid, sebacic acid, Alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof, and succinic acids or anhydrides further substituted with alkyl groups having 6 to 18 carbon atoms; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid Or an anhydride thereof.

Further, glycerin, pentaerythritol, sorbit, sorbitan,
Polyhydric alcohols such as oxyalkylene ether of a novolak type phenol resin are exemplified, and polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydride thereof are exemplified as an acid component.

These polyhydric alcohols and polycarboxylic acids may be contained in an amount of 0.5 to 10 mol%, preferably 1 to 7 mol%, based on all alcohol components or all acid components. The content is more preferably 1.5 to 5 mol%.

The preferred alcohol component of the polyester resin of the present invention is a bisphenol derivative represented by the above formula (A), and the preferred acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-
And dicarboxylic acids such as dodecenylsuccinic acid or its anhydride, fumaric acid, maleic acid and maleic anhydride. Preferable examples of the crosslinking component include trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of a novolak type phenol resin.

Among these, ethylene oxide adduct (hereinafter referred to as EO-BPA) which is a bisphenol derivative represented by the above formula (A) as an alcohol component,
And a propylene oxide adduct (hereinafter referred to as PO-BPA
It is preferable to use EO-BPA / PO-BP if the content ratio is represented by a molar ratio.
A = 0.01 to 10 is preferred, but preferably 0.0
It is the case where it becomes 5-5, More preferably, it is the case where it becomes 0.1-3.

The glass transition temperature (T
g) is 40-80 ° C, preferably 50-70 ° C;
The number average molecular weight (Mn) is adjusted to 2,000 to 40,000, preferably 2,500 to 20,000, and the weight average molecular weight (Mw) is adjusted to 5,000 to 150,000, preferably 6,000 to 80,000. You.

The following are examples of the vinyl-based monomer for producing the vinyl-based resin.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, pn-butylstyrene, p-te
rt-butylstyrene, pn-hexylstyrene, p
-N-octylstyrene, pn-nonylstyrene, p
Styrene and its derivatives such as n-decylstyrene and pn-dodecylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl chloride, vinylidene chloride, and odor. Vinyl halides such as vinyl chloride and vinyl fluoride; vinyl acetate, vinyl propionate,
Vinyl ester acids such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate Α-methylene aliphatic monocarboxylic esters such as phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Methyl ether, vinyl ethyl ether, such as vinyl ethers vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, such as vinyl ketones of methyl isopropenyl ketone; N- vinyl pyrrole, N- vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide or methacrylic acid derivatives;
Esters of unsaturated acids and diesters of dibasic acids.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene; Monomers having a hydroxyl group such as (hydroxy-1-methylhexyl) styrene are exemplified.

Glass transition temperature (Tg) of the vinyl resin
Is preferably 45 to 80 ° C, more preferably 55 to 70 ° C. Number average molecular weight (M
n) is preferably from 2,000 to 50,000, more preferably from 2,500 to 20,000. The weight average molecular weight (Mw) of the vinyl resin is preferably from 5,000 to 200,000, and more preferably from 6,000 to 100,000.

The low molecular weight wax (C) according to the present invention comprises
It is represented by the following general formula.

RY [R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. Specific examples of the compound include (a) CH ₃ (CH ₂ ) _n CH ₂ OH (b) CH ₃ (CH ₂ ) _n CH ₂ COOH (c) CH ₃ (CH ₂ ) _n CH ₂ OCH ₂ ( _{CH 2) m CH 3 (d} ) CH 3 (CH 2) n CH 2 COO (CH 2) m CH 3 (e) CH 3 (CH 2) n CH 2 OSO 3 H (n = about 20 to about 200, m = 0 to about 100). These compounds are derivatives of the compound (a), and the main chain is a linear saturated hydrocarbon. As long as it is a compound derived from the compound (a), those other than those shown in the above examples can also be used.

The above compound has a number average molecular weight (Mn) of 20.
0-2,000, weight average molecular weight (Mw) is 400-
It is preferable that Mw / Mn is 3,000 or less and 3.0 or less. By providing such a molecular weight distribution, the alkyl modification accompanying the increase in the molecular weight of the low-molecular-weight polyester (B) can be improved, and the toner can have preferable physical characteristics. When the molecular weight is smaller than the above range, the composition is susceptible to thermal and mechanical effects excessively, and causes problems in offset resistance and storage stability. On the other hand, when the ratio is larger than the above range, the reaction efficiency is reduced, the unreacted residue of the isocyanate compound adversely affects the toner properties, and the effect of adding the low molecular weight wax is lost.

The low molecular weight wax (C) according to the present invention comprises
In a DSC curve measured by a differential scanning calorimeter,
It shows a maximum endothermic peak in the range of 70 to 130 ° C. when the temperature is raised, and has a maximum exothermic peak when the temperature is lowered in a range of ± 9 ° C. with respect to the peak temperature of the maximum endothermic peak.

In the DSC curve at the time of temperature rise, the low molecular weight wax (C) is melted in the above temperature range, so that it coexists with the volatile components during the production of the toner.
It exerts an appropriate plasticizing effect on the binder resin to give a uniform toner composition. In addition, after the toner is manufactured, the releasing effect of the wax component dispersed uniformly, in addition to the good fixing property, is effectively exhibited, so that a fixing area is secured, and further, the developing characteristics of the toner are improved.

On the other hand, in the DSC curve at the time of temperature decrease, an exothermic peak accompanying the coagulation and crystallization of the low molecular weight wax (C) is observed. The presence of this exothermic peak in a temperature region close to the endothermic peak at the time of temperature increase indicates that the wax component is more homogeneous, and by reducing this difference, the thermal responsiveness of the wax component is reduced. At the same time, a rapid plasticizing effect can be suppressed. Therefore, the wax component according to the present invention, when the toner composition containing the wax component is heated by a fixing device, instantly plasticizes a binder resin described below, and greatly contributes to low-temperature fixing, while significantly contributing to low-temperature fixing. The synergistic effect with the resin can also effectively exert the releasability, and it is possible to achieve both low-temperature fixing property and high-temperature offset resistance at a high level. Further, the dispersion of the wax in a homogeneous state does not adversely affect the triboelectric charging, thereby further improving the developing characteristics of the toner. However, such a wax component has a high recrystallization speed and is liable to cause phase separation. Therefore, dispersion of the wax component, deterioration of the toner due to an external force received from the image forming apparatus, and blooming of the wax component due to long-term storage are caused. As described above, the problem was caused by precisely controlling the amount of the volatile component remaining in the toner composition, and the volatile component contained in the toner component before the wax component was dispersed. By controlling the amount
The dispersion state of each toner component was remarkably improved, and various properties of the toner were remarkably improved.

Particularly preferred as the low molecular weight wax (C) are those having a carbon number distribution of at least 25, more preferably at least 35, especially at least 45 in the carbon number distribution measured by gas chromatography (GC). Are preferred. A low-molecular-weight synthetic wax component in which the peaks appearing according to the number of carbon atoms (one methylene chain) and exhibiting regular strength depending on the number of carbon atoms are easily controlled for the plastic effect, and are preferably used in the present invention.

In order to achieve a good balance of toner characteristics such as development characteristics, fixing properties, and high-temperature offset resistance, the maximum peak should be 25 or more, especially 30 or more, and more preferably 35 to 150. Some are preferably used.

In the present invention, in the DSC measurement, the exchange of heat of the wax is measured and its behavior is observed. Therefore, from the measurement principle, it is preferable to use a highly accurate internal heating input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention is obtained by raising and lowering the temperature once, taking a pre-history, and then setting the temperature rate to 10 ° C./m.
In, a DSC curve measured when the temperature is raised is used.

In the present invention, the molecular weight distribution of the wax is G
It is measured by a PC under the following conditions.

<GPC Measurement Conditions for Wax> Apparatus: GPC-150C (manufactured by Waters) Column: Duplex of GMH-HT (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (added with 0.1% ionol) ) Flow rate: 1.0 ml / min. Sample: 0.4 ml of 0.15% by weight sample is injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

In the present invention, the carbon number distribution of the wax is measured by gas chromatography (GC) under the following conditions.

<GC Measurement Conditions> Apparatus: HP 5890 Series II (manufactured by Yokogawa Electric Corporation) Column: SGE HT-5 6 m × 0.53 mm ID × 0.15 μm Carrier gas: He 20 ml / min Constant Flow Mode Oven temperature : 40 ° C → 450 ° C Inlet temperature: 40 ° C → 450 ° C Detector temperature: 450 ° C Detector: FID Inlet: With pressure control

Under the above conditions, the injection port was pressure-controlled, and the measurement was performed while keeping the optimum flow rate constant, and n-paraffin was used as a standard sample.

It is a preferred embodiment of the present invention to add another low molecular weight wax not represented by the above general formula to the low molecular weight wax (C) in advance.

Other low molecular weight waxes applicable to the present invention include waxy substances such as polypropylene, polyethylene, microcrystalline wax, carnauba wax, sasol wax and paraffin wax;
And their oxides and graft-modified products. These can be used alone or in combination.

The weight average molecular weight of these low molecular weight waxes is 30,000 or less, preferably 10,000 or less. As an addition amount, by using in the range of 20 to 70 parts by weight with respect to 100 parts by weight of the low molecular weight wax (C),
The matching with the low molecular weight polyester (B), the low molecular weight wax (C), and the high molecular weight polymer component (D) is very good, and the object of the present invention can be highly achieved.

The high molecular weight polymer component (D) contained in the binder resin component according to the present invention is a low molecular weight polyester (B).
And a low molecular weight wax (C) having a specific structure and a diisocyanate compound and / or a polyisocyanate compound.

The low molecular weight polyester (B) according to the present invention
In order to improve the reactivity with the isocyanate compound, the hydroxyl value of the low molecular weight polyester (B) is preferably from 10 to 80 mgKOH / g, more preferably from 1 to 80 mgKOH / g.
The composition is adjusted to 0 to 50 mgKOH / g. Hydroxyl value is 1
If it is less than 0 mgKOH / g, the amount of reaction with the isocyanate compound will decrease, making it difficult to form a sufficient high molecular weight region, and resulting in insufficient offset resistance and the like. If it exceeds 60 mgKOH / g, it becomes difficult to increase the molecular weight, and not only the high-temperature offset resistance is deteriorated, but also the toner charging property is adversely affected. Further, since the amount of the isocyanate compound added increases, an unpleasant odor resulting therefrom becomes a new problem.

As the low molecular weight polyester (B), an alcohol component and an acid component of the polyester resin of the low molecular weight polymer component (A) are used.

The low molecular weight polyester (B) may contain a trihydric or higher polyhydric alcohol component or a polyhydric carboxylic acid component as long as the reactivity with the isocyanate compound is not impaired.

Particularly preferred polyhydric alcohol components include, for example, sorbitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol,
Dipentaerythritol, tripentaerythritol,
Sucrose, 1,2,4-menthatriol, glycerin,
2-methylpropanetriol, 2-methyl-1,2,2
4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

Examples of the polycarboxylic acid include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylpropane, 1,3-dicarboxyl-2-methyl-methylenecarboxylpropane, tetra (methylenecarboxyl) methane, , 2,7,8-octanetetracarboxylic acid and their anhydrides.

As the alcohol component of the low molecular weight polyester (B) preferably used in the present invention, a bisphenol derivative represented by the above formula (A) is added so as to be 70 mol% or more of the total alcohol component. Also, at this time,
The molar fraction of EO-BPA / PO-BPA is from 0.01 to
10 is sufficient, but preferably 0.05 to 5, and more preferably 0.1 to 3.

When the molar fraction of EO-BPA / PO-BPA is less than 0.01, the reactivity of the low-molecular-weight polyester (B) decreases, and it is difficult to grow to a sufficient molecular weight. On the other hand, when the molar fraction is more than 10, it becomes difficult to control the growth reaction and the Tg becomes low.

When the above alcohol component is used, particularly preferably used acid components include phthalic acid or its hydrate, terephthalic acid, isophthalic acid, succinic acid, n-
And dicarboxylic acids such as dodecelsuccinic acid or its acid anhydride, fumaric acid, maleic acid, and maleic anhydride.

Examples of the diisocyanate compound and / or polyisocyanate compound which can be reacted with the mixture of the low molecular weight polyester (B) and the low molecular weight wax (C) include the following.

For example, as the diisocyanate compound, trelin diisocyanate (hereinafter referred to as TDI),
Hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate (hereinafter M
DI), xylylene diisocyanate, tetramethyl xylylene diisocyanate, and the like.

The following are examples of the tri- to hexafunctional polyisocyanate compounds.

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The amount of the isocyanate compound to be added depends on the low molecular weight polyester (B) and the low molecular weight wax (C).
0.1 to 1.0 mol equivalent per 1 mol equivalent of hydroxyl group,
Preferably it is 0.15-0.85 mol equivalent. When the addition amount of the isocyanate compound is less than 0.1 mol equivalent, the reaction amount is small, so that it is difficult to form a sufficient high molecular weight region, and the hot offset resistance cannot be satisfied. Also, if it exceeds 1.0 mol equivalent,
Since a remarkable increase in the molecular weight is caused, low-temperature fixability is impaired, and dispersibility of other additives becomes difficult, which adversely affects developability. On the production side, not only the operation becomes difficult due to the increase in viscosity of the resin, but also the grinding efficiency of the toner decreases.

In the present invention, a mixture of a low molecular weight polyester (B) and a low molecular weight wax (C) having a specific structure is reacted with a diisocyanate compound and / or a polyisocyanate compound to produce a high molecular weight polymer component. Examples of the method for obtaining the binder resin according to the present invention include the following methods.

<1> Mixture 10 of low molecular weight polyester (B) and low molecular weight wax (C) having a specific structure
The total amount of the isocyanate compound in an amount of 0.1 to 10 parts by weight with respect to 0 parts by weight is added all at once or continuously little by little. The reaction temperature is in the range of 100 to 200 ° C., and the temperature can be changed stepwise in some cases. The reaction time varies depending on the reaction temperature, but is about 1 minute to 6 hours. And continuous processing using a kneader such as a single-screw or twin-screw extruder. The obtained high molecular weight polymer component (D) is blended with the low molecular weight polymer component (A) by various known methods, and can be used as the binder resin according to the present invention.

<2> The above-described production method except that the isocyanate compound is reacted with a mixture of the low molecular weight polyester (B) and the wax (C) having a specific structure in the presence of the low molecular weight polymer component (A). It can be manufactured in the same manner as in 1).

The binder resin component in the toner according to the present invention comprises:
In the molecular weight distribution of GPC measured by the soluble matter in THF, a low molecular weight component having a molecular weight of 50,000 or less having a main peak in a region of molecular weight of 2,000 to 30,000 and a subpeak or a shoulder in a region of molecular weight of 100,000 or more are present. Those comprising a high molecular weight component having a molecular weight exceeding 50,000 are preferred.

When the peak molecular weight of the high molecular weight component of the binder resin is less than 100,000, not only does the toner not have satisfactory hot offset resistance, but also the wax component according to the present invention has good dispersibility and retention of the dispersed state. Is insufficient, and image defects such as a decrease in image density are likely to occur. Further, when the peak molecular weight of the low molecular weight component of the binder resin is less than 2,000, the plasticization by the wax component becomes abrupt, so that a serious problem occurs in the hot offset resistance and the storage stability. . Further, since phase separation easily occurs locally, the frictional charging of the toner becomes non-uniform, and the developing characteristics deteriorate.
On the other hand, when the peak molecular weight exceeds 30,000, the dispersion state of the wax component is improved to some extent, and although the developing characteristics are improved, the fixability is not sufficient. Further, when the toner is manufactured by a pulverization method or the like, the productivity is reduced.

That is, by specifying the molecular weight distribution of GPC of the binder resin component as described above, it is possible to easily balance various properties required for the toner.

Further, the binder resin component in the toner composition according to the present invention does not substantially contain a THF-insoluble component, and has a molecular weight distribution of not more than 1,000 in the GPC molecular weight distribution measured by the THF-soluble component. The area ratio of the low molecular weight components shown is 15
% And a high molecular weight component having a molecular weight of 1,000,000 or more with an area ratio of 0.5 to 25%, the matching with the wax component according to the present invention becomes very good. That is, when the area ratio of the low molecular weight component having a molecular weight of 1,000 or less exceeds 15%, plasticization is rapidly accelerated by the wax component, and the above-mentioned problem becomes more remarkable. Furthermore, toner fusion to the surface of the photosensitive drum, etc.
There is also a problem in matching with the image forming apparatus. on the other hand,
When the high molecular weight component having a molecular weight of 1,000,000 or more is less than 0.5%, it is difficult to maintain a good dispersion state of the wax component, and the toner is liable to be deteriorated by an external force received from the image forming apparatus. For this reason, the developing characteristics and the storability of the toner, and the durability may be deteriorated. In particular, image fog in a low-temperature and low-humidity environment and a decrease in image density in a high-temperature and high-humidity environment become significant. Conversely, THF insolubles and molecular weight 10
If there are more than 100,000 high molecular weight components in excess of 25%,
In addition to impairing low-temperature fixability and toner productivity, it is difficult to uniformly disperse the toner constituent materials, so that uniform triboelectric charging of the toner cannot be obtained, and the developing characteristics deteriorate. Also,
Even if the mixing force is increased externally by hot-melt kneading etc. during toner production to improve the dispersion state, polymer chains are cut by mechanical shearing force, and balance low-temperature fixability and high-temperature offset resistance It becomes difficult. These tendencies become remarkable especially in a magnetic toner in which the particle diameter of the toner is reduced to a fine particle or magnetic particles having high specific gravity are required to be uniformly dispersed.

Further, in the binder resin component in the toner composition according to the present invention, the high molecular weight component corresponding to a region having a molecular weight of 100,000 or more in the molecular weight distribution of GPC in the THF-soluble component is the same as the low molecular weight polyester (B). ), A mixture of a low molecular weight wax (C) and a high molecular weight polymer component (D) produced by the reaction of an isocyanate compound with the isocyanate compound.
While achieving high low-temperature fixability and high-temperature offset resistance,
Without breaking the balance, the development characteristics and durability of the toner, and further the storage stability and the like can be remarkably improved.

The present inventors consider the reason as follows.

That is, loose crosslinking which is soluble in THF,
Or by including the high molecular weight component having a branched structure in the toner composition, without increasing the melt viscosity of the toner at the time of heat fixing compared to the conventional crosslinkable polymer,
The elasticity of the semi-molten toner can be maintained. Further, the matching with the wax component according to the present invention is good, and the elasticity as described above is not lost even when plasticized. Thereby, the low-temperature fixing property and the high-temperature offset resistance were remarkably improved. Further, by adding a high molecular weight component having the structure as described above, a low melt viscosity portion plasticized by the volatile component or the wax component that is locally phase-separated by undergoing hot melt kneading during toner production. And the uniform mixing force can be enjoyed in the toner composition, so that the dispersion state is synergistically improved and the developing characteristics of the toner are improved. Further, since the mechanical strength of the toner can be increased, it is possible to suppress the deterioration of the toner against external force received from the image forming apparatus, and the matching with the image forming apparatus becomes easy.

In the present invention, the molecular weight distribution of the binder resin component is measured by GPC under the following conditions.

<Measurement conditions for GPC of resin> Apparatus: GPC-150C (manufactured by Waters) Column: KF801 to 7 (manufactured by Shodex) Temperature: 40 ° C Solvent: THF Flow rate: 1.0 ml / min. Sample: 0.1 m of a sample having a concentration of 0.05 to 0.6% by weight
l injection

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken well, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
0.5 μm, for example, Myshoridisk H-25
-5 (manufactured by Tosoh Corporation, Exiclodisk 25CR manufactured by Germanic Science Japan) can be used as a GPC sample. The sample concentration is adjusted so that the resin component has the above concentration.

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample.

The toner composition according to the present invention has a substantially T
Preferably, it does not contain HF insolubles. Specifically, the content is 5% by weight or less, preferably 3% by weight or less based on the resin composition.

The THF-insoluble component in the present invention indicates the weight ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the resin composition in the toner,
It can be used as a parameter indicating the degree of crosslinking of the resin composition containing the crosslinking component. The THF-insoluble matter is defined by a value measured as follows.

That is, 0.5 to 1.0 g of a toner sample was weighed (W ₁ g), and a cylindrical filter paper (No.
86R), subjected to a Soxhlet extractor, extracted with 100 to 200 ml of THF as a solvent for 6 hours, and evaporated the soluble components extracted by the solvent.
After vacuum drying at 100 ° C. for several hours, the amount of the THF-soluble resin component is weighed (W ₂ g). The weight of a component other than the resin component such as a magnetic substance or a pigment in the toner is defined as (W ₃ g). T
The HF insoluble content is obtained from the following equation.

[0103]

(Equation 1)

If the THF-insoluble content exceeds 5% by weight, high-temperature fixing cannot be achieved at a high degree.

In the toner for developing an electrostatic image of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. The charge control agent is a binder resin 100
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
It is preferred to use parts by weight.

Today, charge control agents known in the art include:

For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid, a metal complex, and an aromatic dicarboxylic acid-based metal complex. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples include esters and phenol derivatives of bisphenol.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

As a magnetic material, conventionally, triiron tetroxide (F
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe
₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ -O ₁₂ ), copper iron oxide (CuF
e ₂ O _4), oxidation Tetsunamari (PbFe ₁₂ -O _19), iron oxide nickel (NiFe ₂ O _4), iron oxide, neodymium (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above-mentioned magnetic materials are used alone or in combination of two or more. Particularly suitable magnetic materials for the purposes of the present invention are fine powders of triiron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
When the magnetic properties are about 10 μm and a 10K Oersted is applied, the coercive force is 20 to 150 Oersted, and the saturation magnetization is 50 to 200.
emu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

The magnetic material 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

As the colorant irrespective of one component or two components, carbon black, titanium white, and any other pigments and / or dyes can be used. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6 and the like. Examples of pigments include: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable to improve the sharpness of the pigment in combination with the dye and the pigment in view of the image quality of a full-color image. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other coloring pigments include cyan coloring pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by Chemical Formula 3.

[0116]

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Examples of the coloring pigment for yellow include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the colorant used is 0.1 to 60 parts by weight, preferably 0.5 to 60 parts by weight, based on 100 parts by weight of the binder resin.
50 parts by weight.

As the negatively chargeable fluidizing agent used in the present invention, any material can be used as long as it can be added to the colorant-containing resin particles so that the fluidity can be increased before and after the addition. It is possible. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet-process silica, dry-process silica, etc .; these silicas as silane coupling agents, titanium coupling agents, silicone oils, etc. And the like, surface-treated silica.

Preferred fluidizing agents are fine powders produced by the vapor phase oxidation of silicon halide compounds.
It is what is called dry silica or fumed silica, and is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production step, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide. Is also included. The particle diameter is desirably in the range of 0.001 to 2 μm as an average primary particle diameter, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm. .

Commercially available silica fine powder produced by vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Nippon) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, it is more preferable to use treated silica fine powder obtained by hydrophobizing silica fine powder generated by vapor-phase oxidation of the silicon halide compound. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the fine silica powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

As the fluidizing agent used in the present invention, those obtained by treating the above-mentioned dry-processed silica with a coupling agent having an amino group or silicone oil described below are necessary for achieving the object of the present invention. They may be used accordingly.

[0129]

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[0130]

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As the silicone oil, an amino-modified silicone oil having a partial structure having an amino group in a side chain represented by the following formula is generally used.

[0132]

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(Where R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent a hydrogen, an alkyl group or an aryl group. However, the above alkyl group,
The aryl group, alkylene group and phenylene group may contain an amine, or may have a substituent such as halogen as long as the chargeability is not impaired. m and n are positive integers. )

Examples of the silicone oil having such an amino group include the following.

Viscosity at 25 ° C. Amine Equivalent Trade name (cPs) SF8417 (Toray Silicone Co., Ltd.) 1200 3500 KF393 (Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-3680 (Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-3810B (Shin-Etsu Chemical Co., Ltd.) Shinetsu Gakusha, Ltd.) 1300 1700

The amine equivalent is a value obtained by dividing the molecular weight by the number of amines per molecule in terms of the equivalent per amine (g / equiv).

The fluidizing agent used in the present invention has good results when it has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more measured by nitrogen adsorption according to the BET method. Fluidizer 0.01 for 100 parts by weight of toner
To 8 parts by weight, preferably 0.1 to 4 parts by weight.

To prepare the toner for developing an electrostatic image of the present invention, a binder resin, a colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Then, using a hot kneader such as a kneader or an extruder, melting, kneading and kneading to make the resins compatible with each other. The toner of the present invention can be obtained.

Further, the fluidizing agent and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain the developer for developing an electrostatic image of the present invention having an additive on the surface of the toner particles.

The method for measuring the melting point and molecular weight of the wax used in the toner of the present invention is as follows.

(1) Measurement of melting point of wax Differential thermal analysis measuring device (DSC measuring device), DSC-7
(Perkin Elmer) ASTM D341
Measure according to 8-82.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

The temperature of the endothermic peak is defined as the melting point of the wax. If it is difficult to determine the melting point of the wax, for example, if a sub-peak or shoulder is observed at a temperature near the main peak, the endothermic peak temperature is measured in the same manner as the wax using the toner containing this wax as a measurement sample. The temperature of the main peak is defined as the melting point of the wax.

(2) Measurement of Glass Transition Temperature (Tg) of Binder Resin and Toner A was measured using a differential thermal analyzer (DSC analyzer) and DSC-7 (manufactured by PerkinElmer).
It is measured according to STM D3418-82.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(3) Measurement of molecular weight distribution of wax (GPC measurement conditions) Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0. (1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(4) Measurement of Molecular Weight Distribution of Binder Resin The molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent is passed through the column at this temperature at a flow rate of 1 ml per minute. When the sample is a resin, a resin that has been passed through a roll mill (130 ° C., 15 minutes) is used. When the sample is a developer, the developer is dissolved in THF and then 0.2 μm.
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples. Also, the detector uses RI
A (refractive index) detector is used.

The column used was 10 ³ to 2 × 10
^In order to accurately measure the molecular weight region of ^6, a plurality of commercially available polystyrene gel columns are preferably combined.
μ-styragel 500, 10 manufactured by Aters
Combination of ³ , 10 ⁴ and 10 ⁵ and Showa Denko sho
dex KA-801, 802, 803, 804, 80
A combination of 5,806,807 is preferred.

Next, an image forming method to which the toner of the present invention is applied will be described below with reference to the accompanying drawings.

In the apparatus system shown in FIG. 5, the developing units 54-1, 54-2, 54-3, and 54-4 respectively have a developer containing a cyan toner, a developer containing a magenta toner, and a developer containing a yellow toner. A developer having a developer and a black toner is introduced, and the electrostatic image formed on the electrostatic latent image carrier (for example, the photosensitive drum) 51 is developed by a magnetic brush developing method or a non-magnetic one-component method, and the toner of each color is developed. An image is formed on the photosensitive drum 51.

The toner of the present invention can be mixed with a magnetic carrier and developed using, for example, a developing means as shown in FIG. Specifically, it is preferable to perform development in a state where the magnetic brush is in contact with the photosensitive drum 63 while applying an alternating electric field. Developer carrier (developing sleeve) 6
The distance (S-D distance) B between 1 and the photosensitive drum 63 is 10
A thickness of 0 to 1000 μm is favorable in preventing carrier adhesion and improving dot reproducibility. If it is smaller than 100 μm, the supply of the developer tends to be insufficient and the image density is reduced. If it is larger than 1000 μm, the magnetic field lines from the magnet S1 are widened and the density of the magnetic brush is reduced, resulting in poor dot reproducibility or restrained carrier. And the carrier is likely to adhere.

The voltage (Vpp) between the peaks of the alternating electric field is 5
00 to 5000 V is preferable, and the frequency (f) is 500 to
It is 10,000 Hz, preferably 500 to 3000 Hz, and each can be appropriately selected and used for the process. In this case, the waveforms are triangular, rectangular, sine,
Alternatively, various types of waveforms such as a waveform with a changed duty ratio can be used. If the applied voltage is lower than 500 V, it is difficult to obtain a sufficient image density, and it may not be possible to satisfactorily collect fog toner in the non-image area. 5000
If the voltage exceeds 0 V, the electrostatic image may be disturbed via the magnetic brush, and the image quality may be degraded.

By using a two-component developer having a well-charged toner, the fog removal voltage (Vback) can be reduced.
And the primary charge of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
k is preferably 150 V or less, more preferably 100 V or less, depending on the developing system.

As the contrast potential, 200 V to 500 V is preferably used so that a sufficient image density can be obtained.

If the frequency is lower than 500 Hz, although it depends on the process speed, charge injection into the carrier may occur, and the image quality may be degraded by carrier adhesion or disturbing the latent image. If the frequency exceeds 10,000 Hz, the toner cannot follow the electric field, and the image quality is likely to deteriorate.

In order to obtain a sufficient image density, achieve excellent dot reproducibility, and perform development without carrier adhesion, the contact width (developing nip C) of the magnetic brush on the developing sleeve 61 with the photosensitive drum 63 is preferably set. 3 to 8 mm. If the developing nip C is narrower than 3 mm, it is difficult to sufficiently satisfy a sufficient image density and dot reproducibility.
When the width is larger than mm, packing of the developer occurs to stop the operation of the machine, and it is difficult to sufficiently suppress carrier adhesion. As a method of adjusting the development nip,
The nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 68 and the developing sleeve 61 or adjusting the distance B between the developing sleeve 61 and the photosensitive drum 63.

In the output of a full-color image in which halftone is particularly important, three or more developing devices for magenta, cyan, and yellow are used, and the developer and the developing method of the present invention are used. By combining with a developing system that forms a latent image, it is possible to develop the dot latent image faithfully without being affected by the magnetic brush and disturbing the latent image. In the transfer step, a high transfer rate can be achieved by using the toner of the present invention, so that high image quality can be achieved in both the halftone portion and the solid portion.

Further, by using the toner of the present invention together with the initial improvement of the image quality, the effect of the present invention without deterioration in image quality can be sufficiently exerted even when copying a large number of sheets.

The toner of the present invention can be suitably used for one-component development. An example of an apparatus for developing an electrostatic image formed on an electrostatic latent image carrier is shown, but the invention is not necessarily limited thereto.

In FIG. 7, reference numeral 75 denotes an electrostatic latent image carrier (photosensitive drum), and a latent image is formed by an electrophotographic process means or an electrostatic recording means. Reference numeral 74 denotes a toner carrier (developing sleeve), which is a non-magnetic sleeve made of aluminum, stainless steel, or the like.

The substantially right half peripheral surface of the developing sleeve 74 is always in contact with the toner reservoir in the toner container 71, and the toner near the developing sleeve surface is brought into contact with the developing sleeve surface by the magnetic force of the magnetic generating means in the sleeve. Adhered and held by electrostatic force.

In the present invention, the surface roughness Ra of the toner carrier is
(Μm) is set to 1.5 or less. Preferably it is 1.0 or less. More preferably, it is 0.5 or less.

By controlling the surface roughness Ra to 1.5 or less, the ability of the toner carrier to transport toner particles is suppressed.
Since the toner layer on the toner carrier is made thinner and the number of times of contact between the toner carrier and the toner is increased, the chargeability of the toner is also improved, so that the image quality is synergistically improved.

When the surface roughness Ra of the toner carrier exceeds 1.5, it becomes difficult not only to reduce the thickness of the toner layer on the toner carrier, but also to improve the image quality since the chargeability of the toner is not improved. Can not hope.

In the present invention, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring device (Surfcoder SE-30H, manufactured by Kosaka Laboratory Co., Ltd.) based on JIS surface roughness "JISB 0601". Corresponds to the center line average roughness measured. Specifically, a 2.5 mm portion is extracted from the roughness curve in the direction of the center line as the measurement length a,
The center line of the extracted portion is the X axis, and the direction of the vertical magnification is Y.
When an axis and a roughness curve are represented by y = f (x), a value obtained by the following equation is represented by a micrometer (μm).

[0173]

(Equation 2)

As the toner carrier used in the present invention, a cylindrical or belt-like member made of, for example, stainless steel or aluminum is preferably used. If necessary, the surface may be coated with metal, resin, etc.
A resin in which fine particles such as a resin, metals, carbon black, and a charge controlling agent are dispersed may be coated.

In the present invention, the surface moving speed of the toner carrier is set to be 1.05 to 3 times the surface moving speed of the electrostatic latent image carrier.
By setting it to be 0 times, the toner layer on the toner carrier receives an appropriate stirring effect, so that the faithful reproduction of the electrostatic latent image is further improved.

If the surface moving speed of the toner carrier is less than 1.05 times the surface moving speed of the electrostatic latent image carrier, the stirring effect received by the toner layer becomes insufficient, resulting in good image formation. Can not hope. Also, when developing an image that requires a large amount of toner over a large area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient and the image density is reduced. On the other hand, when it exceeds 3.0, in addition to the various problems caused by excessive charging of the toner as described above,
Deterioration of the toner due to mechanical stress and sticking of the toner to the toner carrier occur and are promoted, which is not preferable.

The toner T is stored in the hopper 71 and is supplied by the supply member 72 onto the developing sleeve. As the supply member, a supply roller made of a porous material such as a foamed material such as a flexible polyurethane foam is preferably used. The supply roller is rotated with respect to the developing sleeve in a forward or reverse direction at a non-zero relative speed, so that the toner is supplied to the developing sleeve and the toner after development (undeveloped toner) on the sleeve is also removed. At this time, the contact width of the supply roller to the developing sleeve is preferably 2.0 to 10.0 mm in consideration of the balance between toner supply and stripping, and 4.0 to 6.0 mm.
mm is more preferable. On the other hand, excessive stress is inevitably applied to the toner, and the aggregation of the toner due to the deterioration of the toner is increased, or the fusion and fixation of the toner to the developing sleeve and the supply roller are easily caused. Is excellent in fluidity and releasability, and has durability stability, so that it is also preferably used in a developing method having the supply member. Further, a brush member made of a resin fiber such as nylon or rayon may be used as the supply member. Although these supply members are extremely effective in a one-component developing method using a non-magnetic one-component toner that cannot utilize a magnetic binding force, they may be used in a one-component developing method using a magnetic one-component toner.

The toner supplied onto the developing sleeve is thinly and uniformly applied by the regulating member. The toner thinning regulating member is a doctor blade such as a metal blade or a magnetic blade disposed at a predetermined gap from the developing sleeve. Or, instead of a doctor blade, use metal,
Rigid rollers or sleeves made of resin, ceramic, or the like may be used, and a magnet generating means may be inserted inside them.

An elastic member such as an elastic blade or an elastic roller for press-applying the toner may be used as a regulating member for thinning the toner. For example, in FIG. 7, an elastic blade 73 has a base on the upper side thereof as a developer container 71.
The developing sleeve 74 is bent in the forward or reverse direction against the elasticity of the blade on the lower side, and the inner surface of the blade (the outer surface in the case of the reverse direction) is the surface of the sleeve 74. To each other with moderate elastic pressure. According to such an apparatus, a dense toner layer that is stable against environmental fluctuations can be obtained. Although the reason is not clear, it is presumed that the elastic body is forcibly rubbed against the surface of the developing sleeve, so that charging is always performed in the same state regardless of a change in behavior due to a change in toner environment.

On the other hand, the toner is apt to be excessively charged and the toner is easily fused to the developing sleeve or the elastic blade. However, the toner used in the present invention is preferable because of its excellent releasability and stable triboelectric charging. Used.

It is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity for the elastic material, and a rubber elastic material such as silicone rubber, urethane rubber, or NBR; a synthetic material such as polyethylene terephthalate. Resin elastic body: Metal elastic bodies such as stainless steel, steel, and phosphor bronze can be used. Further, a composite thereof may be used.

When the elastic body and the toner carrier are required to have durability, it is preferable that the elastic body and the resin or rubber are bonded to the sleeve contact portion or applied by coating.

Further, an organic substance or an inorganic substance may be added to the elastic body, may be melted and mixed, or may be dispersed. For example, the chargeability of the toner can be controlled by adding a metal oxide, metal powder, ceramics, carbon allotrope, whisker, inorganic fiber, dye, pigment, surfactant or the like. Particularly, when the elastic body is a molded body such as rubber or resin, fine particles of metal oxide such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, a charge control agent generally used for toner And the like.

Further, by applying a DC electric field and / or an AC electric field to the developing blade serving as the regulating member, the supply roller serving as the supplying member, and the brush member, the regulating portion on the developing sleeve can be loosened by the toner. In, the uniform thin layer coating property and uniform charging property are further improved,
In the supply portion, the supply / stripping of the toner is performed more smoothly, so that a sufficient image density can be achieved and a high quality image can be obtained.

The contact pressure between the elastic body and the toner carrier is:
The linear pressure in the generatrix direction of the toner carrier is 0.1 kg / m
Above, preferably 0.3 to 25 kg / m, more preferably 0.5 to 12 kg / m is effective. As a result, the aggregation of the toner can be effectively released, and the charge amount of the toner can be instantaneously increased. If the contact pressure is less than 0.1 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fogging and scattering. On the other hand, when the contact pressure exceeds 25 kg / m, a large pressure is applied to the toner, and the toner is undesirably deteriorated and a toner aggregate is generated.
Further, a large torque is required to drive the toner carrier, which is not preferable.

Gap α between electrostatic latent image carrier and toner carrier
Is preferably set to 50 to 500 μm, and the gap between the doctor blade and the toner carrier is preferably set to 50 to 400 μm.

The layer thickness of the toner layer on the toner carrier is most preferably smaller than the gap α between the electrostatic latent image carrier and the toner carrier. Among them, the layer thickness of the toner layer may be restricted to such an extent that a part of the toner layer contacts the electrostatic latent image carrier.

On the other hand, a bias power source 7
By applying an alternating electric field between the toner carrying member and the electrostatic latent image carrying member, the transfer of the toner from the toner carrying member to the electrostatic latent image carrying member can be facilitated, and a higher quality image can be obtained.
Vpp of the alternating electric field is 100 V or more, preferably 200 to
3000V, more preferably 300-2000V. Further, f is 500 to 5000 Hz, preferably 1000 to 3000 Hz, and more preferably 1500
In this case, a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be used as the waveform used in the range of 3000 Hz. Also, asymmetrical AC biases having different positive and reverse voltages and times can be used. It is also preferable to superimpose a DC bias.

In FIG. 5, the electrostatic latent image carrier 51 is aS
e, a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as Cds, ZnO ₂ , OPC, and a-Si. The electrostatic latent image carrier 51 is rotated in a direction indicated by an arrow by a driving device (not shown).

As the electrostatic latent image carrier 51, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having charge transport performance in the same layer.
It may be a single-layer type or a function-separated type photosensitive layer having a charge transport layer as a component of the charge transport layer. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

The binder resin for the organic photosensitive layer is preferably a polycarbonate resin, a polyester resin, or an acrylic resin, particularly having good transferability and cleaning properties, and poor cleaning, fusion of toner to a photoreceptor, and filming of external additives. Less likely.

In the charging step, there are a system that is not in contact with the electrostatic latent image carrier 51 using a corona charger and a contact system that uses a roller or the like, and any of them is used. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 5 is preferably used.

The charging roller 52 basically has a core metal 52b at the center and a conductive elastic layer 52a forming the outer periphery thereof. The charging roller 52 is provided with an electrostatic latent image carrier 51.
The electrostatic latent image carrier 51 is pressed against the surface with a pressing force and is driven to rotate as the electrostatic latent image carrier 51 rotates.

The preferable process conditions when the charging roller is used are that the contact pressure of the roller is 5 to 500 g / cm
When a DC voltage with an AC voltage superimposed is used, the AC voltage is 0.5 to 5 kVpp and the AC frequency is 50 kVpp.
Hz to 5 kHz, the DC voltage is ± 0.2 to ± 1.5 kV, and when only the DC voltage is used, the DC voltage is ± 0.2 to ± 0.5 kV.
2 to ± 5 kV.

Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage is not required and generation of ozone is reduced.

The material of the charging roller and the charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

The toner image on the electrostatic latent image carrier is transferred to the intermediate transfer member 55 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The surface of the electrostatic latent image carrier is cleaned by cleaning means 59 having a cleaning blade 58.

The intermediate transfer member 55 includes a pipe-shaped conductive core 55b and a medium-resistance elastic layer 55 formed on the outer peripheral surface thereof.
a. The core metal 55b may be formed by applying a conductive plating to a plastic pipe.

The medium-resistance elastic layer 55a is made of silicone rubber, Teflon rubber, chloroprene rubber, urethane rubber,
EPDM (terpolymer of ethylene propylene diene)
A conductive material such as carbon black, zinc oxide, tin oxide, or silicon carbide is mixed and dispersed in an elastic material such as to adjust the electric resistance (volume resistivity) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. It is a solid or foamed layer.

The intermediate transfer member 55 is provided in parallel with the electrostatic latent image carrier 51 and is disposed in contact with the lower surface of the electrostatic latent image carrier 51. It rotates in the counterclockwise direction of the arrow at the same peripheral speed as.

The first color toner image formed and carried on the surface of the electrostatic latent image carrier 51 passes through a transfer nip where the electrostatic latent image carrier 51 and the intermediate transfer body 55 are in contact with each other. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 55 by the electric field formed in the transfer nip area by the transfer bias applied to the body 55.

If necessary, the surface of the intermediate transfer member 55 is cleaned by the detachable cleaning means 60 after the transfer of the toner image onto the recording material. When there is a toner image on the intermediate transfer member, the cleaning unit 60 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

A transfer means is provided in parallel with the intermediate transfer body 55 and is brought into contact with the lower surface of the intermediate transfer body 55. The transfer means 57 is, for example, a transfer roller or a transfer belt. It rotates clockwise with the same peripheral speed as the arrow. The transfer means 57 may be provided so as to directly contact the intermediate transfer body 55, or a belt or the like may be provided so as to contact between the intermediate transfer body 55 and the transfer means 57.

In the case of the transfer roller, the basic configuration is a core metal 57b at the center and a conductive elastic layer 57a forming the outer periphery thereof.

For the intermediate transfer member and the transfer roller, general materials can be used. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer body, the voltage applied to the transfer roller can be reduced, and a good toner image can be formed on the transfer material. In addition, it is possible to prevent the transfer material from being wound around the intermediate transfer member. In particular, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer member is at least 10 times the volume resistivity of the elastic layer of the transfer roller.

For example, the conductive elastic layer 5 of the transfer roller 57
7b is a polyurethane in which a conductive material such as carbon is dispersed,
Ethylene-propylene-diene terpolymer (EPD
M) or the like, and is made of an elastic body having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm. A bias is applied to the core metal 57a from a constant voltage power supply. The bias condition is ± 0.
2 to ± 10 kV is preferred.

Since the toner of the present invention has excellent cleaning properties, filming hardly occurs on the electrostatic latent image carrier. Further, even when a multi-sheet durability test is performed, the toner of the present invention has less embedding of the external additive on the surface of the toner particles than the conventional toner, so that good image quality can be maintained for a long time. In particular, it is preferably used in an image forming apparatus having a so-called reuse mechanism that removes transfer residual toner on an electrostatic latent image carrier or an intermediate transfer member by a cleaning unit such as a cleaning blade and reuses the collected transfer residual toner. .

Next, the toner image on the recording material 56 is fixed by a heat and pressure fixing means. As the heating and pressing fixing means, a heating roller incorporating a heating element such as a halogen heater and a pressing roller of an elastic body pressed against the heating roller with a pressing force as a basic configuration, or a heating roller through a film. A method of heating and fixing (FIGS. 2 and 3) can be mentioned, but the toner of the present invention is excellent in fixability and anti-offset property, and thus shows good matching with the above-mentioned heating and pressing fixing means.

[0210]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

Table 1 shows the contents of the wax components used in the present invention together with the measurement results of DSC and GPC.
Put together.

That is, 75 C of higher alcohol of C ₅₀
Polyethylene waxes A and C containing t ₅₀ % and polyethylene waxes B and C ₂₂ containing 67% by weight of higher fatty acids.
Wax C containing a higher alcohol as a main component, and Wax E (for toner addition) obtained by thermal decomposition of polypropylene.

[0213]

[Table 1]

[Production Example 1 of Resin Composition] Synthesis of Low Molecular Weight Polymer (A-1) In a four-necked flask, 46 mol% of isophthalic acid and 5.0 mol% of trimellitic anhydride were represented by the above formula (A). Propylene oxide adduct (PO-BPA) 31 mol%, the same ethylene oxide adduct (EO-BPA) 15 mol%, trimethylolpropane 3.0 mol%, and a small amount of an organotin compound as a dehydration catalyst, The temperature was raised to 220 ° C. while passing nitrogen through the flask, and dehydration-condensation polymerization was performed to obtain a low molecular weight polymer (A-1).

When the obtained low molecular weight polymer (A-1) was analyzed, the weight average molecular weight (Mw) was 8,400,
The number average molecular weight (Mn) is 3,500, and the peak molecular weight (P
Mw) was 4,600, the glass transition temperature (Tg) was 58 ° C., and the hydroxyl value was 5.1 mgKOH / g.

Synthesis of low molecular weight polyester (B-1) 43 mol% of isophthalic acid, 2.0 of trimellitic anhydride
mol%, PO-BPA 30 mol%, EO-BPA
20 mol%, trimethylolpropane 5.0 mol
%, Except that low-molecular-weight polyester (B-1) was obtained.

The obtained low molecular weight polyester (B-1)
Was analyzed, Mw = 8,700, Mn = 4,30
0, PMw = 5,900, and Tg = 23 ° C., the hydroxyl value was 30.9 mgKOH / g.

Production of Resin Composition (I) 60 parts by weight of a low molecular weight polymer (A-1) and 40 parts by weight of a low molecular weight polyester (B-1) pulverized so as to pass through a mesh having a diameter of 1 mm; Low molecular weight wax A
5 parts by weight (represented by a higher alcohol-based wax of CH ₃ (CH ₂ ) ₄₈ CH ₂ OH) was premixed with a Henschel mixer.

[0219] Next, the kneading temperature of the resin mixture, which had been preliminarily mixed, was set to 140 using a quantitative feeder.
° C., to the twin-screw kneader set to be continuously supplied at a predetermined rate so that the average residence time is 15 minutes,
Melt, knead, and mix. At this time, volatile components in the resin are removed from the first vent port provided in the twin-screw kneader by vacuum, and then a predetermined amount of toresin isocyanate (TDI) is discharged from the second vent port using a metering pump. The reaction was continuously fed to advance the reaction. After cooling and solidifying the obtained resin composition, it was pulverized to obtain a resin composition (I).

When the resin composition for toner (I) was analyzed, Mw = 10000, Mn = 2,600, and PMw =
4,700, the THF insoluble content is 11 wt%, and the hydroxyl value of the low molecular weight component having a molecular weight of 50,000 or less is 3.1 mgKOH / g.
Met. In addition, composition analysis of a high molecular weight component having a molecular weight exceeding 50,000 confirmed that it was a reaction product of polyester and TDI.

[Production Example 2 of Resin Composition] Synthesis of low molecular weight polymer (A-2) 37 mol% of isophthalic acid, 13 mol of terephthalic acid
%, PO-BPA 47 mol%, and diethylene glycol 3 mol% except that the low molecular weight polymer (A-
A low molecular weight polymer (A-2) was obtained in the same manner as in the synthesis of 1).

When the obtained low molecular weight polymer (A-2) was analyzed, Mw = 7,600, Mn = 3,400, P
Mw = 4,400, Tg = 57 ° C., and the hydroxyl value was 4.0 mgKOH / g.

Production of Resin Composition (II) Production of the resin composition (I) except that the low molecular weight polymer (A-2) was 60 parts by weight and the low molecular weight polyester (B-1) was 40 parts by weight. In the same manner as in the above, a resin composition for toner (II) was obtained.

When the resin composition for toner (II) was analyzed, Mw = 9,800, Mn = 2,500, PMw
= 4,500, THF insoluble content is 9.3 wt%, and low molecular weight component having a molecular weight of 50,000 or less has a hydroxyl value of 3.4 mg KOH.
/ G. In addition, composition analysis of a high molecular weight component having a molecular weight exceeding 50,000 confirmed that it was a reaction product of polyester and TDI.

[Production Example 3 of Resin Composition] 300 parts by weight of xylene was charged into an autoclave made of a synthetic glass of a low molecular weight polymer (A-3), and the inside of the vessel was sufficiently purged with nitrogen while stirring.
It sealed and heated up to 200 degreeC.

A mixture of 88 parts by weight of styrene, 12 parts by weight of acryl-n-butyl and 2 parts by weight of di-tert-butyl peroxide was added dropwise over 2.5 hours while maintaining the pressure and reflux conditions at the same temperature. After that, the mixture was held for 1 hour to complete the polymerization, thereby obtaining a low molecular weight polymer (A-3).

When the obtained low molecular weight polymer (A-3) was analyzed, Mw = 8,500, Mn = 4,300, P
Mw = 7,000, Tg = 60 ° C., and the hydroxyl value was 0.3 mgKOH / g.

Synthesis of low molecular weight polyester (B-2) 44 mol% of isophthalic acid, 23 mol of PO-BPA
%, Diethylene glycol 30 mol%, and trimethylolpropane 3.0 mol%, except that the synthesis of the low molecular weight polymer (A-1) was carried out to obtain a low molecular weight polyester (B-2).

The obtained low molecular weight polyester (B-2)
Analysis showed that Mw = 8,200 and Mn = 4,40.
0, PMw = 6,000, Tg = 20 ° C., and the hydroxyl value was 28.5 mgKOH / g.

Preparation of Resin Composition (III) In a four-necked flask, 300 parts by weight of xylene, 60 parts by weight of the low-molecular-weight polymer (A-3), and 40 parts by weight of the low-molecular-weight polyester (B-2) Further, 5 parts by weight of the wax component B (a higher fatty acid-based wax having a representative structural formula of CH ₃ (CH ₂ ) ₄₈ COOH) was added. The resin composition was stirred while raising the temperature, and the resin composition was dissolved in xylene. A xylene solution containing 5 parts by weight of diphenylmethane-diisocyanate (MDI) was added dropwise under xylene reflux. After completion of the dropwise addition, stirring was further continued for 1 hour to terminate the reaction, and the solvent was distilled off to obtain a resin composition for toner (III).

When the resin composition for toner (III) was analyzed, Mw = 12,000, Mn = 3,000, PMw
= 7,000, THF insoluble content is 8.1 wt%, and the low molecular weight component having a molecular weight of 50,000 or less has a hydroxyl value of 8.9 mg KOH.
/ G. In addition, composition analysis of a high molecular weight component having a molecular weight exceeding 50,000 confirmed that it was a reaction product of polyester and MDI.

[Production Example 4 of Resin Composition] Synthetic low molecular weight polymer (A-4) 75 parts by weight of styrene, 18 parts by weight of n-butyl acrylate, 7 parts by weight of monobutyl maleate, and di-ter
A low molecular weight polymer (A-4) was obtained in the same manner as in the synthesis of the low molecular weight polymer (A-3) except that 2 parts by weight of t-butyl peroxide was used.

When the obtained low molecular weight polymer (A-4) was analyzed, Mw = 9,000, Mn = 5,200, P
Mw = 6,700, Tg = 59 ° C., hydroxyl value is 2.6
mg KOH / g.

Production of Resin Composition (IV) The above resin composition (III) except that the low molecular weight polymer (A-4) was used instead of the low molecular weight polymer (A-3).
In the same manner as in the production of, a resin composition for toner (IV) was obtained.

When the resin composition for toner (IV) was analyzed, Mw = 13,000, Mn = 2,800, and PMw =
6,800, THF insoluble content is 6.7 wt%, molecular weight 5
The hydroxyl value of low molecular weight components of 10,000 or less is 14.8 mg KOH
/ G. In addition, composition analysis of a high molecular weight component having a molecular weight exceeding 50,000 confirmed that it was a reaction product of polyester and MDI.

[Production Example 1 of Comparative Resin Composition ] As the wax component of the comparative resin composition (i), the above-mentioned wax component (represented by a higher alcohol having a structural formula of CH ₃ (CH ₂ ) ₁₈ CH ₂ OH) Using 5 parts by weight of a wax, the addition amount of MDI to be dropped is 2
A resin composition for comparison (i) was obtained in the same manner as in the resin composition (III) except that the amount was changed to parts by weight.

When the comparative resin composition (i) was analyzed, Mw = 9,400, Mn = 2,900, and PMw =
7,000, THF insoluble content is 2.4 wt%, molecular weight 5
The hydroxyl value of the low molecular weight component of 10,000 or less is 22.0 mg KOH
/ G.

[Production Example 2 of Comparative Resin Composition ] Production of Comparative Resin Composition (ii) In a four-necked flask, 250 parts by weight of xylene, 60 parts by weight of the low-molecular-weight polymer (A-4), Then, 40 parts by weight of the low molecular weight polyester (B-2) were added, and a resin composition for comparison (ii) was obtained in the same manner as in the resin composition (III).

When the comparative resin composition (ii) was analyzed, Mw = 11,000, Mn = 3,100, PMw =
6,600, THF insoluble content is 7.7 wt%, molecular weight 5
The hydroxyl value of the low molecular weight component of 10,000 or less is 22.9 mg KOH
/ G.

[Toner Production Examples and Comparative Production Examples] Production examples and comparative production examples of the toner of the present invention will be described.

Production Example 1 of Toner 100 parts by weight of resin composition (I) obtained in Production Example of Resin 100 parts by weight of magnetic particle powder (spherical, 0.25 μm, bulk density = 0.88 g / cm ³ ) 2 parts by weight of wax D described in Table 1 2 parts by weight of a negative charge control agent (monoazo iron complex represented by the following structural formula)

[0242]

Embedded image

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The powder was classified with a fixed wall air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed by a multi-division classifier utilizing a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) at the same time to remove the weight average particle diameter (D ₄ ). Of 6.4 μm was obtained.

A hydrophobic silica fine powder (BET specific surface area = 300 m ²⁾ treated with 100 parts by weight of the magnetic toner classification powder, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, and then dimethylsilicone oil treatment
/ G) was dry-mixed with a Henschel mixer to obtain 1.2 parts by weight of the toner (1) of the present invention.

Toner Production Examples 2 to 4 and Comparison of Toner
Production Example 1 Except for using the resin compositions (II) to (IV) obtained in Production Examples 2 to 4 of the resin composition and the comparative resin composition (i) obtained in Comparative Production Example 1, Production Example 1 of Toner
In the same manner as in the above, toners (2) to (4) of the present invention and comparative toner (1) were obtained.

Toner Comparative Preparation Example 2 Comparative resin composition (i) obtained in Resin Comparative Preparation Example 2
i) 100 parts by weight, 5 parts by weight of wax B and 2 parts by weight of wax D shown in Table 1, and further, Production Example 1 of the toner
Using 100 parts by weight of the magnetic particle powder and 2 parts by weight of the negative charge control agent, a comparative toner (2) was obtained in the same manner as in Toner Production Example 1.

The toners (1) to (10) of the present invention obtained as described above.
Table 2 summarizes the properties of (4) and the comparative toners (1) and (2).

[0248]

[Table 2]

Examples 1 to 4 and Comparative Examples 1 and 2 The image forming apparatus used in this example will be described. In this embodiment, a commercially available laser beam printer LBP-
PX (manufactured by Canon) was used under the following conditions.

One preferred specific example of the image forming apparatus is shown in FIGS.
This will be described with reference to FIG.

In this embodiment, an example of a reversal developing apparatus for developing a negative (negative) latent image on a photoreceptor using a negative (negative) toner will be described.

FIG. 1 is a schematic explanatory view of a cross section of a laser beam printer applied to the present invention.

OPC photosensitive drum 10 (diameter 24 mm)
Rotates in the direction of the arrow, and is uniformly charged by the charging roll 11 so that the dark portion potential (Vd) becomes −600 V.
Next, the image portion is exposed by the exposure device 14, and an electrostatic latent image having a bright portion potential (V1) of -150V is formed. A gap (300 μm) is set without contact between the photosensitive drum 10 and the developer layer on the toner carrier 16 (including the magnet 17), and an AC bias (f = 1800 Hz, Vpp = 1400)
V) and a DC bias (Vdc = −400 V) were applied to the toner carrier 16 by the bias applying means V, and the image portion was developed with negative toner to form a toner image on the photosensitive drum. Transfer the obtained toner image to a transfer roll 1
9 transfers the toner onto the recording material, and the toner remaining on the surface of the photoreceptor is cleaned by the cleaner 13. On the other hand, the recording material P separated from the photosensitive drum 10 is subjected to a heat fixing process by the heat fixing device H in order to fix a toner image on the recording material P. Image formation is performed by repeating the above steps. At this time, in the heating and fixing device H, the surface temperature of the temperature measuring element 21d of the heating body 21 is 130 ° C., the total pressure between the heating body 21 and the pressure roller 23 is 6 kg, and the nip between the pressure roller and the film is 3 mm. Film 22
A 50 μm thick heat-resistant polyimide film having a low-resistance release layer in which a conductive material is dispersed in PTEF on a contact surface with a recording material was used.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
At 0% Rh) environment, a printout test was performed on 6,000 sheets continuously at a printout speed of 4 sheets (A4 size) / min while supplying the toner according to the present invention and the comparative toner. The obtained images were evaluated for the following items. At the same time, matching between the used image forming apparatus and the toner was also evaluated.

[Evaluation of Printout Image] <1> Image Density 10,000 ordinary paper for ordinary copying machines (75 g / m ² )
Evaluation was made by maintaining the image density at the end of printing out one sheet. The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00.

◎: Very good (1.40 or more) ：: Good (1.35 or more and less than 1.40) Δ: Normal (1.00 or more and less than 1.35) ×: Bad (less than 1.00) )

<2> Dot Reproducibility The pattern shown in FIG. 4 was printed out, and the dot reproducibility was evaluated.

◎: Very good (2 or less defects / 100) ○: Good (3 to 5/100 defects) Δ: Normal (6 to 10/100 defects) ×: Bad (11 defects) Above / 100)

<3> Image fog The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image and the whiteness of the transfer paper measured by a “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). Image fog was evaluated.

◎: Very good (less than 1.5%) ○: Good (1.5% or more, less than 2.5%) Δ: Normal (2.5% or more, less than 4.0%) ×: Poor (4.0% or more)

<4> Fixing Property The fixing property was evaluated by applying a load of 50 g / m ² , rubbing the fixed image with soft thin paper, and decreasing the image density before and after rubbing (%).

◎: Very good (less than 5%) ○: Good (5% or more and less than 10%) Δ: Normal (10% or more, less than 20%) ×: Poor (20% or more)

<5> Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and visually observing the degree of stain on the image after 3000 sheets.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (little effect on image) ×: bad (conspicuous)

[Evaluation of Matching of Image Forming Apparatus] <1> Matching with Developing Sleeve After the printout test was completed, the state of fixation of the residual toner on the surface of the developing sleeve and the effect on the printout image were visually evaluated.

◎: very good (no occurrence) ：: good (almost no occurrence) Δ: normal (there is sticking but little influence on the image) ×: bad (many sticking and image unevenness occurs)

<2> Matching with Photosensitive Drum The occurrence of scratches on the surface of the photosensitive drum and adhesion of residual toner and the effect on printout images were visually evaluated.

◎: very good (not generated) ：: good (slight flaws are seen, but there is no effect on the image) Δ: normal (there is sticking or flaws, but little effect on the image) ×: Bad (Many sticking causes vertical streak-like image defects)

<3> Matching with Fixing Device The state of the surface of the fixing roller was observed, and its durability was evaluated.

(1) Surface Properties The surface of the fixing film surface after the printout test was visually evaluated for scratches and scraping.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (scratch or scraping, but little effect on image) ×: bad (notable)

(2) Status of fixation of residual developer The status of fixation of the residual developer on the surface of the fixing film or the fixing roller after the printout test was visually evaluated.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (there is sticking, but there is little effect on the image) ×: bad (notable)

Tables 3 and 4 summarize the above results.

[0275]

[Table 3]

[0276]

[Table 4]

Production Example 5 of Toner and Comparison of Toner
Production Example 3 Toner Production Example 1 and Comparative toner Production Example 1 except that 10 parts by weight of carbon black (BET specific surface area = 55 m ² / g) was used instead of 100 parts by weight of magnetic particle powder.
The toner (V) of the present invention and the comparative toner (i
ii) was obtained.

Table 5 summarizes the properties of the toner (V) of the present invention and the comparative toner (iii) obtained above.

[0279]

[Table 5]

The above toner (V) and comparative toner (ii)
i) was mixed with 7 parts by weight of each and 93 parts by weight of a resin-coated magnetic ferrite carrier (average particle size = 55 μm) to prepare a two-component developer for magnetic brush development (A) and a developer for comparison (a). Prepared.

Example 5 and Comparative Example 3 An image forming apparatus used in this example will be described.

In the present embodiment, a reversal developing apparatus having an intermediate transfer member will be described as an example.

FIG. 5 is a schematic explanatory view of a cross section of a color copying machine applied to the present invention.

The photosensitive drum 51 has a photosensitive layer 51b having an organic optical semiconductor on a base material 51a, and rotates in the direction of the arrow to oppose and rotate in contact with the charging roller 52 (conductive elastic layer 52a, core metal 52b). ) To charge the photosensitive drum 51 to a surface potential of about -600 V. The exposure 53 is turned on and off on the photoreceptor by a polygon mirror in accordance with digital image information, thereby forming an electrostatic image having an exposed portion potential of -100 V and a dark portion potential of -600 V. A toner image was obtained on the photoreceptor 51 using any one of the plurality of developing devices 54-1, 54-2, 54-3, and 54-4 by a reversal developing method. The toner image is transferred onto the intermediate transfer member 55 (the elastic layer 55a and the core metal 55b as a support), and a four-color superimposed developed image is formed on the intermediate transfer member 55. The transfer material toner on the photoconductor 51 is collected in a residual toner container 59 by the cleaner member 58.

The intermediate transfer member 55 has a pipe-shaped core 55b.
An elastic layer 55 on which a carbon black conductivity-imparting member is sufficiently dispersed in nitrile-butadiene rubber (NBR).
b. The hardness of the coat layer 55b is
Based on "JIS K-6301", it was 30 degrees and the volume resistivity was 10 ⁹ Ω · cm. The transfer current required for transfer from the photoreceptor 51 to the intermediate transfer member 55 was about 5 μA, which was obtained by applying +500 V from the power supply to the cored bar 55b.

The transfer roller 57 has an outer diameter of 20 mm and a diameter of 10 mm.
a conductive property providing member made of ethylene-propylene-diene-based terpolymer (EPDM)
Has an elastic layer 57a formed by coating a material which is sufficiently dispersed in a foamed material having a volume resistivity of 10 ⁶ Ω · cm.
The reference hardness of "6301" was 35 degrees. A voltage was applied to the transfer roller, and a transfer current of 15 μA was passed.

As the heat fixing device H, a heat roll type fixing device having no oil application function was used. At this time, both the upper roller and the lower roller had a fluororesin surface layer, and the diameter of the roller was 60 mm. The fixing temperature was set at 160 ° C., and the nip width was set at 7 mm.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
0% RH) in a single-color continuous mode (that is, while replenishing the developer (A) and the comparative developer (a) sequentially at a printout speed of 6 sheets (A4 size) / min.
A printout test was performed in a mode in which the consumption of toner was promoted without stopping the developing device), and the obtained printout image was evaluated for the following items.

The matching between the image forming apparatus used at the same time and the developer was also evaluated.

The residual toner collected by the cleaning was transported to a developing device by a reuse mechanism and reused.

Tables 6 and 7 summarize the above evaluation results.

[0292]

[Table 6]

[0293]

[Table 7]

[0294]

As described above, according to the present invention,
By specifying each component constituting the binder resin, it has a good fixable temperature range, and has excellent dot reproduction,
A stable and good toner image without fog could be formed for a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an image forming apparatus used in an embodiment of the present invention.

FIG. 2 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 3 is an enlarged cross-sectional view of a main part showing a film state when the fixing device used in the embodiment of the present invention is not driven.

FIG. 4 is an explanatory diagram of a checker pattern for checking development characteristics of toner.

FIG. 5 is a schematic explanatory view of an image forming apparatus used in an embodiment of the present invention.

FIG. 6 is an enlarged cross-sectional view of a main part of a developing device for a two-component developer used in an embodiment of the present invention.

FIG. 7 is an enlarged cross-sectional view of a main part of a developing device for a one-component developer used in an embodiment of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 electrostatic latent image carrier (photosensitive drum) 11 charger (charging roll) 12 cartridge 13 cleaning means 14 exposure means 15 developer container 16 toner carrier (development sleeve) 17 magnetic field generating means 18 elastic layer thickness regulating member DESCRIPTION OF SYMBOLS 19 Transfer means (transfer roll) 20 Stay 21 Heating body 21a Heater substrate 21b Heating body 21c Surface protection layer 21d Temperature measuring element 22 Fixing film 23 Pressure roller 24 Coil spring 25 Film end regulating flange 26 Power supply connector 27 Disconnecting member 28 Inlet Guide 29 Exit guide (separation guide)

Claims (31)

[Claims] 1. An electrostatic image developing toner containing at least a binder resin and a colorant, wherein the binder resin of the toner comprises: (a) substantially free of tetrahydrofuran (THF) -insoluble matter; ) In the molecular weight distribution of gel permeation chromatography (GPC) of the THF-soluble component, i) the hydroxyl value of the low molecular weight component corresponding to the region having a molecular weight of 50,000 or less is 20 (mgKOH / g) or less; ii) the molecular weight of 5 The high molecular weight component corresponding to more than 10,000 regions is a polymer obtained by reacting a mixture of a low molecular weight polyester and a low molecular weight wax having the following general formula with a diisocyanate compound and / or a polyisocyanate compound. Y [R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] A toner for developing an electrostatic image. 2. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000, and a weight average molecular weight (Mn).
2. The electrostatic image developing toner according to claim 1, wherein w) is 400 to 3,000, and Mw / Mn is 3.0 or less. 3. A DSC curve measured by a differential scanning calorimeter shows that the wax component has a viscosity of 70 to 13 at the time of temperature rise.
3. The electrostatic charge according to claim 1, wherein a maximum endothermic peak is shown in a region of 0 ° C., and a maximum exothermic peak at the time of temperature decrease is in a range of ± 9 ° C. with respect to a peak temperature of the maximum endothermic peak. Image developing toner. 4. A main peak is formed in a molecular weight distribution of 2000 to 30,000 in a molecular weight distribution of gel permeation chromatography (GPC) measured by a tetrahydrofuran (THF) soluble component of a binder resin in the toner. The electrostatic image development according to any one of claims 1 to 3, comprising a low molecular weight polymer component and a high molecular weight polymer component forming a subpeak or a shoulder in a region exceeding a molecular weight of 50,000. For toner. 5. The binder resin in the toner is substantially TH
In the molecular weight distribution of GPC containing no F-insoluble component and THF-soluble component, the area ratio of the low molecular weight component having a molecular weight of 1,000 or less is 15% or less, and the high molecular weight component having a molecular weight of 1,000,000 or more is used. The toner according to any one of claims 1 to 4, wherein an area ratio is 0.5 to 25%. 6. A charging step of applying a voltage to a charging member from the outside to charge an object to be charged, a step of forming an electrostatic charge image on the charged object to be charged, and a step of converting the electrostatic charge image with toner. An image having a developing step of developing to form a toner image on a member to be charged, a transfer step of transferring the toner image on the member to be charged to a recording material, and a fixing step of heating and fixing the toner image on the recording material A method of forming the toner, wherein the toner contains at least a binder resin and a colorant, and the binder resin of the toner contains (a) substantially no tetrahydrofuran (THF) -insoluble matter, and (b) In the molecular weight distribution of the gel soluble permeation chromatography (GPC) of the THF-soluble component, i) the hydroxyl value of the low molecular weight component corresponding to the region having a molecular weight of 50,000 or less is 20 (mgKOH / g) or less; ii) the molecular weight of 50,000 To The high molecular weight component corresponding to the region obtained is a polymer obtained by reacting a mixture of a low molecular weight polyester and a low molecular weight wax having the following general formula with a diisocyanate compound and / or a polyisocyanate compound. R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] An image forming method characterized in that: 7. The heating and fixing step in which a toner image is heat-fixed to a recording material by a heating and fixing device that does not supply an offset preventing liquid or does not have a fixing device cleaner. 2. The image forming method according to 1., 8. The recording material according to claim 1, wherein said heating and fixing step comprises: a heating member fixed and supported; and a pressing member which is in pressure contact with said heating member and closely adheres to said heating member via a film. 8. The heat fixing method according to claim 6, wherein
2. The image forming method according to 1., 9. The method according to claim 6, wherein in the charging step, the charging member is brought into contact with the member to be charged, and a voltage is externally applied to the charging member to charge the member to be charged. 2. The image forming method according to 1., 10. A process for developing an electrostatic latent image on an electrostatic latent image carrier with toner and transferring the toner image to a recording material electrostatically via a transfer device. The image forming method according to claim 6, wherein the body and the transfer device are in contact with each other. 11. A developing device in which a coating layer containing conductive fine particles is formed on the surface of a toner carrier that transports toner to a developing area formed between the carrier and the electrostatic latent image carrier. The image forming method according to claim 6, wherein: 12. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (M).
The image forming method according to claim 6, wherein w) is 400 to 3,000, and Mw / Mn is 3.0 or less. 13. A DSC curve measured by a differential scanning calorimeter, wherein the wax component has a viscosity of 70 to 1 upon heating.
13. The method according to claim 6, wherein a maximum endothermic peak is shown in a region of 30 ° C., and a maximum exothermic peak at the time of temperature fall is in a range of ± 9 ° C. with respect to a peak temperature of the maximum endothermic peak. Image forming method. 14. A main peak is formed in a region having a molecular weight of 2,000 to 30,000 in a molecular weight distribution of gel permeation chromatography (GPC) measured by a tetrahydrofuran (THF) soluble component of a binder resin in the toner. The low molecular weight polymer component and a high molecular weight polymer component forming a subpeak or a shoulder in a region exceeding a molecular weight of 50,000 are characterized in that they are contained.
3. The image forming method according to any one of 3. 15. The binder resin in the toner is substantially T
In the molecular weight distribution of GPC containing no HF-insoluble component and THF-soluble component, the area ratio of the low-molecular-weight component having a molecular weight of 1,000 or less is 15% or less, and the high-molecular-weight component having a molecular weight of 1,000,000 or more is used. The image forming method according to any one of claims 6 to 14, wherein the area ratio is 0.5 to 25%. 16. A charging step of applying a voltage to a charging member from the outside to charge a member to be charged, a step of forming an electrostatic image on the charged member, and a step of forming the electrostatic image by toner. A developing step of developing to form a toner image on the member to be charged, a first transfer step of transferring the toner image on the member to be charged to the intermediate transfer member, and transferring the toner image on the intermediate transfer member to a recording material An image forming method comprising: a second transfer step of transferring; and a fixing step of heating and fixing a toner image on a recording material, wherein the toner contains at least a binder resin and a colorant. The binder resin contains (a) substantially no tetrahydrofuran (THF) -insoluble matter, and (b) a molecular weight distribution of gel-permeation chromatography (GPC) of the THF-soluble matter, i) a region having a molecular weight of 50,000 or less. Low equivalent to Ii) a high molecular weight component corresponding to a region having a molecular weight exceeding 50,000 is a mixture of a low molecular weight polyester and a low molecular weight wax having the following general formula, and a diisocyanate compound; And / or RY which is a polymer obtained by a reaction with a polyisocyanate compound [R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] An image forming method characterized in that: 17. The method according to claim 16, wherein in the heat fixing step, the toner image is heat-fixed to the recording material by a heat fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. 2. The image forming method according to 1., 18. The recording medium according to claim 18, wherein the heating and fixing step comprises: a heating member fixed and supported; and a pressing member which is in pressure contact with the heating member and closely adheres to the heating member via a film. The image forming method according to claim 16, wherein the image is fixed by heating. 19. The method according to claim 16, wherein in the charging step, the charging member is brought into contact with the member to be charged, and a voltage is externally applied to the charging member to charge the member to be charged. 2. The image forming method according to 1., 20. Use of a developing device in which a coating layer containing conductive fine particles is formed on the surface of a toner carrier that transports toner to a developing area formed between the electrostatic latent image carrier and the toner carrier. The image forming method according to claim 16, wherein: 21. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (M
21. The image forming method according to claim 16, wherein w) is 400 to 3,000 and Mw / Mn is 3.0 or less. 22. The DSC curve of the wax component, which is measured by a differential scanning calorimeter, is 70 to 1 when the temperature is raised.
22. A maximum endothermic peak is shown in a region of 30 ° C., and a maximum exothermic peak at the time of temperature fall is in a range of ± 9 ° C. with respect to a peak temperature of the maximum endothermic peak.
The image forming method according to any one of the above. 23. A main peak is formed in a molecular weight distribution region of 2000 to 30,000 in a molecular weight distribution of gel permeation chromatography (GPC) measured by a tetrahydrofuran (THF) soluble component of a binder resin in the toner. 23. The image forming method according to claim 16, further comprising a low molecular weight polymer component and a high molecular weight polymer component forming a subpeak or a shoulder in a region having a molecular weight exceeding 50,000. 24. The binder resin in the toner is substantially T
In the molecular weight distribution of GPC containing no HF-insoluble component and THF-soluble component, the area ratio of the low-molecular-weight component having a molecular weight of 1,000 or less is 15% or less, and the high-molecular-weight component having a molecular weight of 1,000,000 or more is used. 24. The image forming method according to claim 16, wherein an area ratio is 0.5 to 25%. 25. A resin composition for a toner used in a toner for developing an electrostatic image, wherein the binder resin component of the resin composition for the toner comprises: (a) a tetrahydrofuran (THF) -insoluble content of 30 wt.
(B) in the molecular weight distribution of gel-permeation chromatography (GPC) of the THF-soluble component, i) a low molecular weight polymer having a hydroxyl value of 20 mg KOH / g or less and a molecular weight of 50,000 or less, and ii) a low molecular weight. Polymer RY [R: R represents a hydrocarbon group] obtained by reacting a mixture of polyester and a low molecular weight wax having the following general formula with a diisocyanate compound and / or a polyisocyanate compound. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ], And a resin composition for toner. 26. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (M
26. The resin composition for a toner according to claim 25, wherein w) is 400 to 3,000 and Mw / Mn is 3.0 or less. 27. A DSC curve measured by a differential scanning calorimeter, which shows that the wax component has a viscosity of 70 to 1 upon heating.
27. The method according to claim 25, wherein a maximum endothermic peak is shown in a region of 30 ° C., and a maximum exothermic peak when the temperature is lowered is in a range of ± 9 ° C. with respect to a peak temperature of the maximum endothermic peak.
3. The resin composition for toner according to item 1. 28. A method for producing a resin composition used in a toner for developing an electrostatic image, wherein the resin composition comprises a mixture of a low molecular weight polyester and a low molecular weight wax having the following general formula, and a diisocyanate compound: Or, by reacting a polyisocyanate compound, (a) tetrahydrofuran (THF) insoluble matter is 30 wt.
(B) in a molecular weight distribution of gel-permeation chromatography (GPC) of a THF-soluble component, i) a low molecular weight polymer corresponding to a region having a molecular weight of not more than 50,000 and having a hydroxyl value of not more than 20 mgKOH / g; ii) A high-molecular-weight polymer RY [corresponding to a region exceeding a molecular weight of 50,000 obtained by reacting a mixture of a low-molecular-weight polyester and a low-molecular-weight wax having the following general formula with a diisocyanate compound and / or a polyisocyanate compound. R: represents a hydrocarbon group. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] At the same time. 29. The method for producing a resin composition for a toner according to claim 28, wherein the reaction is carried out in the presence of a low molecular weight polymer having a hydroxyl value of 20 mgKOH / g or less. 30. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000, and a weight average molecular weight (M
30. The method for producing a resin composition for a toner according to claim 28, wherein w) is 400 to 3,000 and Mw / Mn is 3.0 or less. 31. In a DSC curve measured by a differential scanning calorimeter, the wax component has a viscosity of 70 to 1 upon heating.
31. A maximum endothermic peak is shown in a region of 30 ° C., and a maximum exothermic peak at the time of temperature fall is in a range of ± 9 ° C. with respect to a peak temperature of the maximum endothermic peak.
The method for producing a resin composition for a toner according to any one of the above.